(a). Field of the Invention
The present invention relates to metallocene compounds, metallocene catalysts including the compounds and methods of polymerizing olefins with the catalysts.
(b). Description of the Related Art
Catalysts including transition metals have been widely used for olefin polymerization. Lately, German Patent Nos. 2,608,933 and 3,007,725 have disclosed that metallocene compound consisting of Group 4B transition metal such as zirconium, titanium or hafnium, and ligand having cyclopentadienyl structure can be used as catalyst for olefin polymerization in the presence of an activator such as methylaluminoxane. The examples of the ligands having the cyclopentadienyl structures include cyclopentadiene, indene, fluorene, and substituted varieties of such compounds.
Various metallocene compounds having cyclopentadienyl-type ligands have been used to prepare the catalyst systems for the olefin polymerization. It has also been known that changes of chemical structures of the cyclopentadienyl ligands may produce significant effects on the suitabilities of metallocene compounds as the catalysts. For example, activities, stereospecificities, and stabilities of the catalysts, and physical properties of the polymers obtained by the polymerization depend on the sizes and positions of substituents bonded to cyclopentadienyl ligands.
In various documents such as European patent No. 129,368, U.S. Pat. Nos. 4,874,880 and 5,324,800 and Makromol. Chem. Rapid Commun., 4, 417(1983) et al., it have also been disclosed that the catalyst systems including of metallocene compounds, which consists of substituted-cyclopentadienyl ligands and zirconium as the transition metal, and methylaluminoxane have high activities in the olefin polymerization. In addition, the metallocene compounds consisting of zirconium and cyclopentadienyl ligands substituted with hydrocarbyl group are also known. For examples, bis(alkylcyclopentadienyl) zirconium dichloride (wherein, alkyl represents methyl, ethyl, isopropyl, tert-butyl or trimethylsilyl.) [J. Chem. Soc. Dalton Trans.,805(1981)], bis(pentamethylcyclopentadienyl)zirconium dichloride [J. Amer. Chem. Soc., 100, 3078(1978)], (pentamethylcyclopentadienyl) (cyclopentadienyl)zirconium dichloride [J. Amer. Chem. Soc., 106, 6355(1984)], bis(di, tri, or tetra alkyl-cyclopentadienyl)zirconium dichloride [U.S. Pat. No. 4,874,880], non-bridged metallocene compounds having substituted indenyl ligands [U.S. Pat. No. 5,780,659], metallocene compounds having mono substituted cyclopentadienyl ligand [German patent No. 4,312,270] are known.
Even though the activities of the metallocene catalysts have been progressively increased by changing the structures of the metallocene compounds, there exists a need for the better metallocene catalysts having sufficient activities to prepare polyolefin of high molecular weight and better physical properties.
Thus, the present invention is directed to the preparation of polyolefin with novel catalyst systems, which include metallocene compounds consisting of cyclopentadienyl-type ligands having silacycloalkyl substituents and transition metal such as zirconium, titanium or hafnium.
It is, therefore, an object of the present invention to provide novel metallocene compounds, which forms metallocene catalysts for olefin polymerization.
It is another object of the present invention to provide new metallocene catalysts prepared from the metallocene compounds.
It is also another object of the present invention to provide methods of polymerizing olefins with the metallocene catalysts.
In accordance with an embodiment of the present invention, there is provided metallocene compounds of the following formula 1 or 2, which can be used to prepare metallocene catalysts for olefin polymerization.
(CpR1aRsb)(Cpxe2x80x2R2axe2x80x2Rsbxe2x80x2)MX2xe2x80x83xe2x80x83[Formula 1]

In formula 1 and 2, Cp and Cpxe2x80x2, which can be the same or different, represent a radical selected from the group consisting of cyclopentadienyl radical, indenyl radical, 4,5,6,7-tetrahydro-1-indenyl radical and fluorenyl radical;
R1 and R2, which can be the same or different, represent phosphine, amino, alkyl having 1 to 20 carbon atoms, alkoxy, alkylamino, dialkylamino, alkoxy-alkyl, aryl, aryloxy-alkyl, alkenyl, alkylaryl or arylalkyl radical;
Rs represents 1-alkyl-1-silacyclohydrocarbyl radical of the following formula 3,
wherein, R3 and R4, which can be the same or different, represent hydrogen or alkyl radical having 1 to 5 carbon atoms, R5 is alkyl radical having 1 to 8 carbon atoms, and n is an integer of 4 to 8;
Cpxe2x80x2R2axe2x80x2, Rsbxe2x80x2 in the formula 2 can be displaced with divalent NRxe2x80x3 radical, wherein Rxe2x80x3 represents Rs, alkyl radical having 1 to 12 carbon atoms, or aryl radical having 6 to 10 carbon atoms;
M represents a Group 4B, 5B, 6B transition metal, and preferably represents titanium, zirconium or hafnium;
X, which can be the same or different, represents one radical selected from the group consisting of halogen, alkyl radical having 1 to 20 carbon atoms, aryl, alkenyl, alkylaryl, arylalkyl, alkoxy and aryloxy radicals; and
Q represents alkylene radical having 1 to 4 carbon atoms, dialkyl germanium or silicon, alkyl phosphine or amine radical, bis-dialkylsilyl or bis-dialkylgermanyl having hydrocarbyl radical of 1 to 4 carbon atoms.
In formula 1, a is an integer of 0 to 4, axe2x80x2 is an integer of 0 to 5, b is an integer of 1 to 3, and bxe2x80x2 is an integer of 0 to 3, wherein 1xe2x89xa6a+bxe2x89xa65, 0xe2x89xa6axe2x80x2+bxe2x80x2xe2x89xa65; and in formula 2, a is an integer of 0 to 3, axe2x80x2 is an integer of 0 to 4, b is an integer of 1 to 2, and bxe2x80x2 is an integer of 0 to 3, wherein 1xe2x89xa6a+bxe2x89xa64, 0xe2x89xa6axe2x80x2+bxe2x80x2xe2x89xa64.
In accordance with another embodiment of the present invention, there is provided metallocene catalysts comprising:
at least one metallocene compound selected from the compounds represented by formula 1 or 2; and
at least one activator selected from the group consisting of aluminoxanes represented by the following formula 4 or 5, aromatic boron compounds substituted with fluoride, and modified clays. 
In the formula 4 and 5, Rxe2x80x2, which can be the same or different, represent hydrocarbyl radical having 1 to 10 carbon atoms, x is an integer of 1 to 50, and y is an integer of 3 to 50.
In accordance with another embodiment of the present invention, there is provided methods of polymerizing olefins with the metallocene catalysts comprising:
at least one metallocene compound selected from the compounds represented by formula 1 or 2; and
at least one activator selected from the group consisting of aluminoxanes represented by the following formula 4 or 5, aromatic boron compounds substituted with fluoride, and modified clays.
The methods of polymerizing olefins preferably include liquid phase polymerization, slurry phase polymerization or gas phase polymerization.
The present invention will be illustrated in detail by the following preferred embodiments.
The present invention is to provide methods of polymerizing olefins in the presence of the metallocene catalysts comprising at least one metallocene compounds of the formula 1 or 2, which consist of cyclopentadienyl-type ligands substituted with silacycloalkyl radical and a Group 4B, 5B, 6B transition metal. Hereinafter, the method for preparing the metallocene compounds of the present invention will be described step by step in detail, and then the preferable examples of metallocene compounds of the present invention will be provided.
The metallocene compounds, (CpR1aRSb)2MX2, which is a compound of formula 1 when CpR1aRSb is the same with Cpxe2x80x2R2axe2x80x2Rsbxe2x80x2, can be prepared by the following 7 steps.
Step 1 is to produce a compound represented by RsXxe2x80x2 by reacting Xxe2x80x2(CR3R4)nSi(R5)Xxe2x80x22 with magnesium according to the well known cyclization reaction shown in the following reaction scheme 1.
In reaction scheme 1, Rs represents 1-alkyl-1-silacyclohydrocarbyl radical of the above formula 3, R3 and R4, which can be the same or different, represent hydrogen or alkyl radical having 1 to 5 carbon atoms, R5 is alkyl radical having 1 to 8 carbon atoms, n is an integer of 4 to 8, and Xxe2x80x2 is Cl, Br or I.
The following reaction scheme 2 is a example for preparing the compound of RsXxe2x80x2 according to the step 1, and is disclosed in J. Amer. Chem. Soc., 89,1144(1967) and J. Organometal. Chem., 43,121(1972). 
In reaction scheme 2, Xxe2x80x2, R5 and Rs represent same radicals defined in the reaction scheme 1.
The reaction may be performed in the presence of the solvent of diethyl ether at a temperature of 0 to 60xc2x0 C. for 1 to 15 days. To separate the compound of RsXxe2x80x2 from the reaction product, which is a mixture of liquid and solid phase, the liquid phase is filtered and fractional-distilled to obtain the compound of RsXxe2x80x2, or the product can be directly fractional-distilled to obtain the compound of RsXxe2x80x2. Since the 1-alkyl-1-silacyclohydrocarbyl halide(RsXxe2x80x2) has so high boiling point that it is difficult to separate it and its yield is very low, the separating process should be very precisely controlled.
Accordingly, to obtain the compound of RsXxe2x80x2 with high yield, two or more traps can be connected with the reactor to separate the liquid phase from the solid material under vacuum, and then pure 1-alkyl-1-silacyclohydrocarbyl halide (RsXxe2x80x2) can be obtained by slow fractional-distillation of the liquid phase.
In step 2, Mxe2x80x2(CpR1a) or Li(CpR1a) is obtained by reacting the compound CpR1a with alkali metal Mxe2x80x2 (for example, sodium or potassium) or metallating agent such as alkyl lithium (for example, butyl lithium), and the obtained Mxe2x80x2 (CpR1a) or Li(CpR1a) reacts with the compound RsXxe2x80x2 to produce CpR1aRs as shown in the following reaction scheme 3.
In reaction scheme 3, Cp represents a radical selected from the group consisting of cyclopentadienyl radical, indenyl radical, 4,5,6,7-tetrahydro-1-indenyl radical and fluorenyl radical. R1a, which are substituted to Cp and can be the same or different, represent phosphine, amino, alkyl having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl and the like), alkoxy, alkylamino, dialkylamino, alkoxy-alkyl, aryl, aryloxy-alkyl, alkenyl, alkylaryl or arylalkyl radical, and preferably is alkyl radical having 1 to 6 carbon atoms. xe2x80x9caxe2x80x9d is an integer of 0 to 4, and Rs and Xxe2x80x2 represent same radicals defined in the reaction scheme 1.
The compound CpR1a can be prepared according to any conventional method. The compound CpR1a is converted into the corresponding metal compound Na(CpR1a), K(CpR1a) or Li(CpR1a) by the reaction with a metallating agent such as Na, K or alkyl lithium. The conversion into such metal compound may be generally performed under inert gas atmosphere such as nitrogen and in the presence of solvent at xe2x88x9278 to 60xc2x0 C. for 2 to 40 hours. The solvent used in the process may include diethyl ether, diethyleneglycol diethylether, letrahydrofuran (THF), pentane, hexane, heptane and the like. More preferable solvent includes diethyl ether, tetrahydrofuran (THF), pentane or hexane. The obtained organometallic compound may be directly used in the next reaction step, or may be separated and kept in the form of solid powder for the use in the next step.
The reaction of the organometallic compound Na(CpR1a), K(CpR1a) or Li(CPR1a) with the compound (RsXxe2x80x2) can be carried out in the presence of the solvent such as diethyl ether, tetrahydrofuran (THF), pentane, hexane or the like at a temperature of xe2x88x9278 to 70xc2x0 C. for 2 to 28 hours. After the reaction is complete, the next reaction step can be directly performed in the same reactor, or the precipitate of metal salt can be removed by filtration or centrifugation, and the ligand compound of (CpR1aRs) having the cyclopentadienyl structure can be obtained through purification.
Step 3 is to prepare the compound Li(CpR1aRs) by reacting CpR1aRs produced in step 2 with metallating agent such as alkyl lithium (for example, butyl lithium) as shown in the following reaction scheme 4.
The reaction step 3 may be performed in the presence of solvent at a temperature of xe2x88x9278 to 60xc2x0 C. for 2 to 40 hours. The solvent for the reaction may include diethyl ether, diethyleneglycol diethylether, tetrahydrofuran (THF), pentane, hexane, heptane, or the like. More preferable examples of the solvents include diethyl ether, tetrahydrofuran (THF), pentane or hexane. The resultant organometallic compound may be directly used in the next reaction, or may be separated and kept in the form of solid powder for the use in the next step.
Step 4 is to prepare the compound (CpR1aRs)2MX2 by reacting Li(CpR1aRs) produced in the step 3 with MX4 as shown in the following reaction scheme 5.
In step 4, the organometallic compound Li(CpR1aRs) is mixed and reacted with the transition metal halide MX4 in the presence of solvent, wherein M represents a Group 4B, 5B, 6B transition metal, and X represents halogen. The more preferable transition metal M includes titanium, zirconium or hafnium, and more preferable halogen X includes Cl, Br or I. The reaction may be performed in the presence of solvent at a temperature of xe2x88x9278 to 60xc2x0 C. for 1 hour to 3 days. The suitable solvent for reaction step 4 includes diethyl ether, diethyleneglycol diethylether, tetrahydrofuran (THF), dichloromethane, and the like. The obtained product (CpR1aRs)2MX2 can be purified through evaporation of the solvent, filtration, and recrystallization or sublimation.
The compound Li(CpR1aRsb) can be prepared by repeating steps 2 and 3, and (CpR1aRsb)2MX2 can be prepared by carrying out the step 4 with the compound Li(CpR1aRsb). When CpR1aRsb is different from Cpxe2x80x2R2axe2x80x2Rsbxe2x80x2 in the metallocene compounds of the formula 1, Li(CpR1aRsb) is reacted with (Cpxe2x80x2R2axe2x80x2Rsbxe2x80x2)M3 to obtain (CpRhu 1aRsb)(Cpxe2x80x2R2axe2x80x2Rsbxe2x80x2)MX2. Namely, to prepare the asymmetric metallocene compounds of the formula 1 in which CpR1aRsb is different from Cpxe2x80x2R2axe2x80x2Rsbxe2x80x2, Li(CpR1aRsb) and (Cpxe2x80x2R2axe2x80x2RSbxe2x80x2)MX3 are dissolved into solvent with same equivalent and mixed for reaction. Cpxe2x80x2 and R2 have same meanings with Cp and R1, and can be same or different with Cp and R1, respectively, and axe2x80x2 is an integer of 0 to 5. b is an integer of 1 to 3, and bxe2x80x2 is an integer of 0 to 3, wherein 1xe2x89xa6a+bxe2x89xa65, 0xe2x89xa6axe2x80x2+bxe2x80x2xe2x89xa65.
This reaction may be performed in the presence of solvent at a temperature of xe2x88x9278 to 60xc2x0 C. for 1 hour to 3 days. The solvent used in the reaction may include diethyl ether, diethyleneglycol diethyl ether, tetrahydrofuran (THF), dichloromethane. The product produced by the reaction can be purified through evaporation of the solvent, filtration, and recrystallization or sublimation.
The method of preparing the metallocene compounds of the formula 2 in the case of CpR1aRsbxe2x80x2 being same with Cpxe2x80x2R2axe2x80x2Rsb will be described in detail, below. The metallocene compounds of the formula 2 can be prepared through the same steps 1, 2 and 3 as in the preparation of the metallocene compounds of the formula 1, and further through steps 5 to 7, which will be described below.
Step 5 is to react the product of the step 3 with one or more compounds represented by X1QX2 as shown in the following reaction scheme 6. 
In reaction scheme 6, X1 and X2, which can be the same or different, represent Cl, Br, I or xe2x80x94OSO2R6(example: -O-tosyl radical), and R6 represents alkyl radical having 1 to 6 carbon atoms or aryl radical having 6 to 10 carbon atoms.
In this reaction, the organometallic compound Li(CpR1aRs) produced in the step 3 is reacted with one or more bridging agents X1QX2 according to the reaction scheme 6 to obtain a bridged compound, in which the two cyclopentadienyl compounds CpR1aRS are cross-linked with each other through the functional group Q, which represents alkylene radical having 1 to 4 carbon atoms, dialkyl germanium or silicon, alkyl phosphine or amine radical, bis-dialkylsilyl or bis-dialkylgermanyl having hydrocarbyl radical of 1 to 4 carbon atoms. Typical examples of the compound X1QX2 may include 1,2-dibromoethane (BrCH2CH2Br) and dichlorodimethylsilane (Me2SiCl2) [Angew. Chem., Int. Ed. Engl. 777, 18(1979); J. Organometal. Chem., 64, C37(1974); J. Organometal. Chem., 173, 175(1979); J. Organometal. Chem., 232, 233(1982); J. Organometal. Chem., 369, 359(1989); Chem. Lett., 1853(1989)].
This reaction may be performed in the presence of solvent at a temperature of xe2x88x9278 to 70xc2x0 C. for 2 to 48 hours. After completion of this reaction, the obtained compound can be directly used in the next reaction, or the precipitate of metal salt can be removed by filtration or centrifugation, and the bridged ligand compound (CpR1aRs)2Q can be obtained through purification. The solvent used in the reaction may include diethyl ether, tetrahydrofuran (THF), and dichloromethane.
Step 6 is to react the product of the step 5 with metallating agent such as alkyl lithium to obtain the compound Li2(CpR1aRs)2Q as shown in the reaction scheme 7.
The step 7 for preparing the metallocene compound of the formula 2, is to react the compound of Li2(CpR1aRs)2Q produced by the step 6 with transition metal halide MX4 to obtain the compound of Q(CpR1aRs)2MX2 as shown in the reaction scheme 8.
This reaction may be performed in the presence of solvent at a temperature of xe2x88x9278 to 70xc2x0 C. for 4 to 48 hours. After completion of this reaction, the product of Q(CpR1aRs)2MX2 can be purified through evaporation of the solvent, filtration, and recrystallization or sublimation. The suitable solvent includes diethyl ether, tetrahydrofuran (THF), and dichloromethane.
The compound represented by Li(CpR1aRsb) can be prepared by repeating steps 2 and 3, and Q(CpR1aRsb)MX2 can be prepared by carrying out the step 5, 6 and 7 with the compound Li(CpR1aRsb). When CpR1aRsb is lo different from Cpxe2x80x2R2axe2x80x2Rsbxe2x80x2 in the metallocene compounds of the formula 2, the steps 6 and 7 are performed using (CpR1aRsb)Q(Cpxe2x80x2R2axe2x80x2Rsbxe2x80x2) instead of Q(CPR1aRsb)2. In this case, a is an integer of 0 to 3, axe2x80x2 is an integer of 0 to 4, b is an integer of 1 to 2, and bxe2x80x2 is an integer of 0 to 3, wherein 1xe2x89xa6a+bxe2x89xa64, 0xe2x89xa6axe2x80x2+bxe2x80x2xe2x89xa64.
The typical and non-limiting examples of the metallocene compounds of the formula 1 or 2, in the case where the transition metal is zirconium, include
bis((1-methyl-1-silacyclobutyl)-cyclopentadienyl)zirconium dichloride,
bis((1-ethyl-1-silacyclobutyl)-cyclopentadienyl)zirconium dichloride,
bis((1-propyl-1-silacyclobutyl)-cyclopentadienyl)zirconium dichloride,
bis((1-butyl-1-silacyclobutyl)-cyclopentadienyl)zirconium dichloride,
bis(1-methyl-3-(1-methyl-1-silacyclobutyl)-cyclopentadienyl)zirconium dichloride,
bis(1-methyl-3-(1-ethyl-1-silacyclobutyl)-cyclopentadienyl)zirconium dichloride,
bis(1-methyl-3-(1-propyl-1-silacyclobutyl)-cyclopentadienyl)zirconium dichloride,
bis(1-methyl-3-(1-butyl-1-silacyclobutyl)-cyclopentadienyl)zirconium dichloride,
bis(1-ethyl-3-(1-methyl-1-silacyclobutyl)-cyclopentadienyl)zirconium dichloride,
bis(1-ethyl-3-(1-ethyl-1-silacyclobutyl)-cyclopentadienyl)zirconium dichloride,
bis(1-ethyl-3-(1-propyl-1-silacyclobutyl)-cyclopentadienyl)zirconium dichloride,
bis(1-(1-butyl-1-silacyclobutyl)-3-ethyl-cyclopentadienyl)zirconium dichloride,
bis(1-butyl-3-(1-methyl-1-silacyclobutyl)-cyclopentadienyl)zirconium dichloride,
bis(1-butyl-3-(1-ethyl-1-silacyclobutyl)-cyclopentadienyl)zirconium dichloride,
bis(1-butyl-3-(1-propyl-1-silacyclobutl)-cyclopentadienyl)zirconium dichloride,
bis(1-butyl-3-(1-butyl-1-silacyclobutyl)-cyclopentadienyl)zirconium dichloride,
bis(1-(1-methyl-1-silacyclobutyl) indenyl) zirconium dichloride,
bis(1-(1-ethyl-1-silacyclobutyl)indenyl)zirconium dichloride,
bis(1-(1-propyl-1-silacyclobutyl)-indenyl)zirconium dichloride,
bis(1-(1-butyl-1-silacycl obutyl)indenyl)zirconium dichloride,
bis(1-(1-methyl-1-silacyclobutyl)tetrahydroindenyl)zirconium dichloride,
bis(1-(1-ethyl-1-silacyclobutyl)tetrahydroindenyl)zirconium dichloride,
bis(1-(1-propyl-1-silacyclobutyl)tetrahydroindenyl)zirconium dichloride,
bis(1-(1-butyl-1-silacyclobutyl)tetrahydroindenyl)zirconium dichloride,
bis(9-(1-methyl-1-silacyclobutyl)fluorenyl)zirconium dichloride,
bis(9-(1-ethyl-1-silacyclobutyl)fluorenyl)zirconium dichloride,
bis(9-(1-propyl-1-silacyclobutyl)fluorenyl)zirconium dichl oride,
bis(9-(1-butyl-1-silacyclobutyl)fluorenyl)zirconium dichloride,
(1-(1-methyl-1-silacyclobutyl)indenyl)(cyclopentadienyl)zirconium dichloride,
(1-(1-ethyl-1-silacyclobutyl)indenyl)(cyclopentadienyl)zirconium dichloride,
(1-(1-propyl-1-silacyclobutyl)indenyl)(cyclopentadienyl)zirconium dichloride,
(1-(1-butyl-1-silacyclobutyl)indenyl)(cyclopentadienyl)zirconium dichloride,
(1-(1-methyl-1-silacyclobutyl)tetrahydroindenyl)(cyclopentadienyl)zirconium dichloride,
(1-(1-ethyl-1-silacyclobutyl)tetrahydroindenyl)(cyclopentadienyl)zirconium dichloride,
(1-(1-propyl-1-silacyclobutyl)tetrahydroindenyl)(cyclopentadienyl)zirconium dichloride,
(1-(1-butyl-1-silacyclobutyl)tetrahydroindenyl)(cyclopentadienyl)zirconium dichloride,
(1-(1-methyl-1-silacyclobutyl)indenyl)(pentamethylcyclopentadienyl)zirconium dichloride,
(1-(1-ethyl-1-silacyclobutyl)indenyl)(pentamethylcyclopentadienyl)zirconium dichloride,
(1-(1-propyl-1-silacyclobutyl)indenyl)(pentamethylcyclopentadienyl)zirconium dichloride,
(1-(1-butyl-1-silacyclobutyl)indenyl)(pentamethylcyclopentadienyl)zirconium dichloride,
(1-(1-methyl-1-silacyclobutyl)pentahydroindenyl)(pentamethylcyclopentadienyl)zirconium dichloride,
(1-(1-ethyl-1-silacyclobutyl)pentahydroindenyl)(pentamethylcyclopentadienyl)zirconium dichloride,
(1-(1-propyl-1-silacyclobutyl)pentahydroindenyl)(pentamethylcyclopentadienyl)zirconium dichloride,
(1-(1-butyl-1-silacyclobutyl) pentahydroindenyl)(pentamethylcyclopentadienyl)zirconium dichloride,
(1-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)zirconium dichloride,
(1-(1-ethyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)zirconium dichloride,
(1-(1-propyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)zirconium dichloride,
(1-(1-butyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)zirconium dichloride,
(1-methyl-3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)zirconium dichloride,
(1-(1-ethyl-1-silacyclobutyl)-3-methyl-cyclopentadienyl)(cyclopentadienyl)zirconium dichloride,
(1-(1-propyl-1-silacyclobutyl)-3-methyl-cyclopentadienyl)(cyclopentadienyl)zirconium dichloride,
(1-(1-butyl-1-silacyclobutyl)-3-methyl-cyclopentadienyl)(cyclopentadienyl)zirconium dichloride,
((1-methyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride,
((1-ethyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride,
((1-propyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride,
((1-butyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride,
(1-methyl-3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclo pentadienyl)zirconium dichloride,
(1-(1-ethyl-1-silacyclobutyl)-3-methyl-cyclopentadienyl)(pentamethylcyclo pentadienyl)zirconium dichloride,
(1-methyl-3-(1-propyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclo pentadienyl) zirconium dichloride,
(1-(1-butyl-1-silacyclobutyl)-3-methyl-cyclopentadienyl)(pentamethylcyclo pentadienyl) zirconium dichloride,
bis(9-(1-methyl-1-silacyclobutyl)-fluorenyl) zirconium dichloride,
bis(9-(1-ethyl-1-silacyclobutyl)-fluorenyl) zirconium dichloride,
bis(9-(1-propyl-1-silacyclobutyl)-fluorenyl) zirconium dichioride,
bis(9-(1-butyl-1-silacyclobutyl)-fluorenyl) zirconium dichloride,
(9-(1-methyl-1-silacyclobutyl)-fluorenyl)(cyclopentadienyl) zirconium dichloride,
(9-(1-ethyl-1-silacyclobutyl)-fluorenyl)(cyclopentadienyl) zirconium dichloride,
(9-(1-propyl-1-silacyclobutyl)-fluorenyl)(cyclopentadienyl) zirconium dichloride,
(9-(1-butyl-1-silacyclobutyl)-fluorenyl)(cyclopentadienyl) zirconium dichloride,
(9-(1-methyl-1-silacyclobutyl)-fluorenyl)(pentamethylcyclopentadienyl) zirconium dichloride,
(9-(1-ethyl-1-silacyclobutyl)-fluorenyl)(pentamethylcyclopentadienyl) zirconium dichloride,
(9-(1-propyl-1-silacyclobutyl)-fluorenyl)(pentamethylcyclopentadienyl) zirconium dichloride,
(9-(1-butyl-1-silacyclobutyl)-fluorenyl)(pentamethylcyclopentadienyl) zirconium dichloride,
dimethylsilyl(1-(1-methyl-1-silacyclobutyl)cyclopentadienyl) (tert-butylamido) zirconium dichloride,
dimethylsilyl(1-(1-methyl-1-silacyclobutyl)cyclopentadienyl) (sec-butylamido) zirconium dichloride,
ethylene-bis(1-(1-methyl-1-silacyclobutyl)indenyl)zirconium dichloride,
ethylene-bis(1-(1-ethyl-1-silacyclobutyl)indenyl)zirconium dichloride,
ethylene-bis(1-(1-propyl-1-silacyclobutyl)indenyl)zirconium dichloride,
ethylene-bis(1-(1-butyl-1-silacyclobutyl)indenyl)zirconium dichloride,
ethylene-bis(1-(1-methyl-1-silacyclobutyl)tetrahydroindenyl)zirconium dichloride,
ethylene-bis(1-(1-ethyl-1-silacyclobutyl)tetrahydroindenyl)zirconium dichloride,
ethylene-bis(1-(1-propyl-1-silacyclobutyl)tetrahydroindenyl)zirconium dichloride,
ethylene-bis(1-(1-butyl-1-silacyclobutyl)tetrahydroindenyl)zirconium dichloride,
2,2-propyl-bis(3-(1-methyl-1-silacyclobutyl)-1-indenyl)zirconium dichloride,
2,2-propyl-bis(3-(1-ethyl-1-silacyclobutyl)-1-indenyl)zirconium dichloride,
2,2-propyl-bis(3-(1-butyl-1-silacyclobutyl)-1-indenyl)zirconium dichloride,
2,2-propyl-bis(3-(1-methyl-1-silacyclobutyl)-1-tetrahydroindenyl)zirconium dichloride,
2,2-propyl-bis(3-(1-ethyl-1-silacyclobutyl)-1-tetrahydroindenyl)zirconium dichloride,
2,2-propyl-bis(3-(1-butyl-1-silacyclobutyl)-1-tetrahydroindenyl)zirconium dichloride,
ethylene-bis(3-(1-methyl-1-silacyclobutyl) cyclopentadienyl) zirconium dichloride,
2,2-propyl-bis(3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)zirconium dichloride,
2,2-propyl-(3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)zirconium dichloride,
2,2-propyl-(3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(pentamethyl cyclopentadienyl) zirconium dichloride.
The typical and non-limiting examples of the metallocene compounds of the formula 1 or 2, in the case where the transition metal is titanium, include
bis((1-methyl-1-silacyclobutyl)-cyclopentadienyl)titanium dichloride,
bis((1-ethyl-1-silacyclobutyl)-cyclopentadienyl)titanium dichloride,
bis((1-propyl-1-silacyclobutyl)-cyclopentadienyl)titanium dichloride,
bis((1-butyl-1-silacyclobutyl)-cyclopentadienyl)titanium dichloride,
bis(1-methyl-3-(1-methyl-1-silacyclobutyl)-cyclopentadienyl)titanium dichioride,
bis(1-methyl-3-(1-ethyl-1-silacyclobutyl)-cyclopentadienyl)titanium dichloride,
bis(1-methyl-3-(1-propyl-1-silacyclobutyl)-cyclopentadienyl)titanium dichloride,
bis(1-methyl-3-(1-butyl-1-silacyclobutyl)-cyclopentadienyl)titanium dichloride,
bis(1-ethyl-3-(1-methyl-1-silacyclobutyl)-cyclopentadienyl)titanium dichloride,
bis(1-ethyl-3-(1-ethyl-1-silacyclobutyl)-cyclopentadienyl)titanium dichloride,
bis(1-ethyl-3-(1-propyl-1-silacyclobutyl)-cyclopentadienyl)titanium dichloride,
bis(1-(1-butyl-1-silacyclobutyl)-3-ethyl-cyclopentadienyl)titanium dichloride,
bis(1-butyl-3-(1-methyl-1-silacyclobutyl)-cyclopentadienyl)titanium dichloride,
bis(1-butyl-3-(1-ethyl-1-silacyclobutyl)-cyclopentadienyl)titanium dichloride,
bis(1-butyl-3-(1-propyl-1-silacyclobutyl)-cyclopentadienyl)titanium dichloride,
bis(1-butyl-3-(1-butyl-1-silacyclobutyl)-cyclopentadienyl)titanium dichloride,
bis(1-(1-methyl-1-silacyclobutyl)indenyl)titanium dichloride,
bis(1-(1-ethyl-1-silacyclobutyl)-indenyl)titanium dichloride,
bis(1-(1-propyl-1-silacyclobutyl)-indenyl)titanium dichloride,
bis(1-(1-butyl-1-silacyclobutyl)-indenyl)titanium dichloride,
bis(1-(1-methyl-1-silacyclobutyl)tetrahydroindenyl)titanium dichloride,
bis(1-(1-ethyl-1-silacyclobutyl) tetrahydroindenyl)titanium dichloride,
bis(1-(1-propyl-1-silacyclobutyl) tetrahydroindenyl)titanium dichloride,
bis(1-(1-butyl-1-silacyclobutyl) tetrahydroindenyl)titanium dichloride,
bis(9-(1-methyl-1-silacyclobutyl)fluorenyl)titanium dichloride,
bis(9-(1-ethyl-1-silacyclobutyl)fluorenyl)titanium dichloride,
bis(9-(1-propyl-1-silacyclobutyl)fluorenyl)titanium dichloride,
bis(9-(1-butyl-1-silacyclobutyl)fluorenyl)titanium dichloride,
(1-(1-methyl-1-silacyclobutyl)indenyl)(cyclopentadienyl)titanium dichloride,
(1-(1-ethyl-1-silacyclobutyl)indenyl)(cyclopentadienyl)titanium dichloride,
(1-(1-propyl-1-silacyclobutyl)indenyl)(cyclopentadienyl)titanium dichloride,
(1-(1-butyl-1-silacyclobutyl)indenyl)(cyclopentadienyl)titanium dichloride,
(1-(1-methyl-1-silacyclobutyl)tetrahydroindenyl)(cyclopentadienyl)titanium dichloride,
(1-(1-ethyl-1-silacyclobutyl)tetrahydroindenyl)(cyclopentadienyl)titanium dichloride,
(1-(1-propyl-1-silacyclobutyl)tetrahydroindenyl)(cyclopentadienyl)titanium dichloride,
(1-(1-butyl-1-silacyclobutyl)tetrahydroindenyl)(cyclopentadienyl)titanium dichloride,
(1-(1-methyl-1-silacyclobutyl)indenyl)(pentamethylcyclopentadienyl)titanium dichloride,
(1-(1-ethyl-1-silacyclobutyl)indenyl)(pentamethylcyclopentadienyl)titanium dichloride,
(1-(1-propyl-1-silacyclobutyl)indenyl)(pentamethylcyclopentadienyl)titanium dichloride,
(1-(1-butyl-1-silacyclobutyl)indenyl)(pentamethylcyclopentadienyl)titanium dichloride,
(1-(1-methyl-1-silacyclobutyl)pentahydroindenyl)(pentamethylcyclopentadienyl)titanium dichcoride,
(1-(1-ethyl-1-silacyclobutyl)pentahydroindenyl)(pentamethylcyclopentadienyl)titanium dichloride,
(1-(1-propyl-1-silacyclobutyl)pentahydroindenyl)(pentamethylcyclopentadienyl)titanium dichloride,
(1-(1-butyl-1-silacyclobutyl)pentahydroindenyl)(pentamethylcyclopentadienyl)titanium dichloride,
(1-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)titanium dichloride,
(1-(1-ethyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)titanium dichloride,
(1-(1-propyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)titanium dichloride,
(1-(1-butyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)titanium dichloride,
(1-methyl-3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)titanium dichioride,
(1-(1-ethyl-1-silacyclobutyl)-3-methyl-cyclopentadienyl)(cyclopentadienyl)titanium dichloride,
(1-(1-propyl-1-silacyclobutyl)-3-methyl-cyclopentadienyl)(cyclopentadienyl)titanium dichloride,
(1-(1-butyl-1-silacyclobutyl)-3-methyl-cyclopentadienyl)(cyclopentadienyl)titanium dichloride,
((1-methyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclopentadienyl)titanium dichloride,
((1-ethyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclopentadienyl)titanium dichloride,
((1-propyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclopentadienyl)titanium dichloride,
((1-butyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclopentadienyl)titanium dichloride,
(1-methyl-3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclo pentadienyl) titanium dichloride,
(1-(1-ethyl-1-silacyclobutyl)-3-methyl-cyclopentadienyl)(pentamethylcyclo pentadienyl) titanium dichloride,
(1-methyl-3-(1-propyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclo pentadienyl) titanium dichloride,
(1-(1-butyl-1-silacyclobutyl)-3-methyl-cyclopentadienyl)(pentamethylcyclo pentadienyl) titanium dichloride,
bis(9-(1-methyl-1-silacyclobutyl)-fluorenyl) titanium dichloride,
bis(9-(1-ethyl-1-silacyclobutyl)-fluorenyl) titanium dichloride,
bis(9-(1-propyl-1-silacyclobutyl)-fluorenyl) titanium dichloride,
bis(9-(1-butyl-1-silacyclobutyl)-fluorenyl) titanium dichloride,
(9-(1-methyl-1-silacyclobutyl)-fluorenyl)(cyclopentadienyl) titanium dichloride,
(9-(1-ethyl-1-silacyclobutyl)-fluorenyl)(cyclopentadienyl) titanium dichloride,
(9-(1-propyl-1-silacyclobutyl)-fluorenyl)(cyclopentadienyl) titanium dichloride,
(9-(1-butyl-1-silacyclobutyl)-fluorenyl)(cyclopentadienyl) titanium dichloride,
(9-(1-methyl-1-silacyclobutyl)-fluorenyl)(pentamethylcyclopentadienyl) titanium dichtoride,
(9-(1-ethyl-1-silacyclobutyl)-fluorenyl)(pentamethylcyclopentadienyl) titanium dichloride,
(9-(1-propyl-1-silacyclobutyl)-fluorenyl)(pentamethylcyclopentadienyl) titanium dichloride,
(9-(1-butyl-1-silacyclobutyl)-fluorenyl)(pentamethylcyclopentadienyl) titanium dichloride,
dimethylsilyl(1-(1-methyl-1-silacyclobutyl)cyclopentadienyl) (tert-butylamido)titanium dichloride,
dimethylsilyl(1-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(sec-butylamido)titanium dichloride,
ethylene-bis(1-(1-methyl-1-silacyclobutyl)indenyl)titanium dichloride,
ethylene-bis(1-(1-ethyl-1-silacyclobutyl)indenyl)titanium dichloride,
ethylene-bis(1-(1-propyl-1-silacyclobutyl)indenyl)titanium dichloride,
ethylene-bis(1-(1-butyl-1-silacyclobutyl)indenyl)titanium dichloride,
ethylene-bis(1-(1-methyl-1-silacyclobutyl)tetrahydroindenyl)titanium dichioride,
ethylene-bis(1-(1-ethyl-1-silacyclobutyl)tetrahydroindenyl)titanium dichloride,
ethylene-bis(1-(1-propyl-1-silacyclobutyl)tetrahydroindenyl)titanium dichloride,
ethylene-bis(1-(1-butyl-1-silacyclobutyl)tetrahydroindenyl)titanium dichloride,
2,2-propyl-bis(3-(1-methyl-1-silacyclobutyl)-1-indenyl)titanium dichloride,
2,2-propyl-bis(3-(1-ethyl-1-silacyclobutyl)-1-indenyl)titanium dichloride,
2,2-propyl-bis(3-(1-butyl-1-silacyclobutyl)-1-indenyl)titanium dichloride,
2,2-propyl-bis(3-(1-methyl-1-silacyclobutyl)-1-tetrahydroindenyl)titanium dichloride,
2,2-propyl-bis(3-(1-ethyl-1-silacyclobutyl)-1-tetrahydroindenyl)titanium dichloride,
2,2-propyl-bis(3-(1-butyl-1-silacyclobutyl)-1-tetrahydroindenyl)titanium dichloride,
ethylene-bis(3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)titanium dichloride,
2,2-propyl-bis(3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)titanium dichloride,
2,2-propyl-(3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)titanium dichloride,
2,2-propyl-(3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(pentamethyl cyclopentadienyl)titanium dichloride.
The typical and non-limiting examples of the metallocene compounds of the formula 1 or 2, in the case where the transition metal is hafnium, include
bis((1-methyl-1-silacyclobutyl)-cyclopentadienyl)hafnium dichloride,
bis((1-ethyl-1-silacyclobutyl)-cyclopentadienyl)hafnium dichloride,
bis((1-propyl-1-silacyclobutyl)-cyclopentadienyl)hafnium dichloride,
bis((1-butyl-1-silacyclobutyl)-cyclopentadienyl)hafnium dichloride,
bis(1-methyl-3-(1-methyl-1-silacyclobutyl)-cyclopentadienyl)hafnium dichloride,
bis(1-methyl-3-(1-ethyl-1-silacyclobutyl)-cyclopentadienyl)hafnium dichloride,
bis(1-methyl-3-(1-propyl-1-silacyclobutyl)-cyclopentadienyl)hafnium dichloride,
bis(1-methyl-3-(1-butyl-1-silacyclobutyl)-cyclopentadienyl)hafnium dichloride,
bis(1-ethyl-3-(1-methyl-1-silacyclobutyl)-cyclopentadienyl) hafnium dichloride,
bis(1-ethyl-3-(1-ethyl-1-silacyclobutyl)-cyclopentadienyl)hafnium dichloride,
bis(1-ethyl-3-(1-propyl-1-silacyclobutyl)-cyclopentadienyl)hafnium dichloride,
bis(1-(1-butyl-1-silacyclobutyl)-3-ethyl-cyclopentadienyl)hafnium dichloride,
bis(1-butyl-3-(1-methyl-1-silacyclobutyl)-cyclopentadienyl)hafnium dichloride,
bis(1-butyl-3-(1-ethyl-1-silacyclobutyl)-cyclopentadienyl)hafnium dichloride,
bis(1-butyl-3-(1-propyl-1-silacyclobutyl)-cyclopentadienyl)hafnium dichloride,
bis(1-butyl-3-(1-butyl-1-silacyclobutyl)-cyclopentadienyl)hafnium dichloride,
bis(1-(1-methyl-1-silacyclobutyl)indenyl)hafnium dichloride,
bis(1-(1-ethyl-1-silacyclobutyl)indenyl)hafnium dichloride,
bis(1-(1-propyl-1-silacyclobutyl)indenyl)hafnium dichloride,
bis(1-(1-butyl-1-silacyclobutyl)indenyl)hafnium dichloride,
bis(1-(1-methyl-1-silacyclobutyl)tetrahydroindenyl)hafnium dichloride,
bis(1-(1-ethyl-1-silacyclobutyl) tetrahydroindenyl)hafnium dichloride,
bis(1-(1-propyl-1-silacyclobutyl) tetrahydroindenyl)hafnium dichloride,
bis(1-(1-butyl-1-silacyclobutyl) tetrahydroindenyl)hafnium dichloride,
bis(9-(1-methyl-1-silacyclobutyl)fluorenyl)hafnium dichloride,
bis(9-(1-ethyl-1-silacyclobutyl)fluorenyl)hafnium dichloride,
bis(9-(1-propyl-1-silacyclobutyl)fluorenyl) hafnium dichloride,
bis(9-(1-butyl-1-silacyclobutyl)fluorenyl)hafnium dichloride,
(1-(1-methyl-1-silacyclobutyl)indenyl)(cyclopentadienyl)hafnium dichloride,
(1-(1-ethyl-1-silacyclobutyl)indenyl)(cyclopentadienyl)hafnium dichloride,
(1-(1-propyl-1-silacyclobutyl)indenyl)(cyclopentadienyl)hafnium dichloride,
(1-(1-butyl-1-silacyclobutyl)indenyl)(cyclopentadienyl)hafnium dichloride,
(1-(1-methyl-1-silacyclobutyl)tetrahydlroinden yl)(cyclopentadienyl)hafnium dichloride,
(1-(1-ethyl-1-silacyclobutyl)tetrahydroindenyl)(cyclopentadienyl)hafnium dichloride,
(1-(1-propyl-1-silacyclobutyl)tetrahydroindenyl)(cyclopentadienyl)hafnium dichloride,
(1-(1-butyl-1-silacyclobutyl)tetrahyd roindenyl)(cyclopentadienyl)hafnium dichloride,
(1-(1-methyl-1-silacyclobutyl) indenyl)(pentamethylcyclopentadienyl)hafnium dichloride,
(1-(1-ethyl-1-si lacyclobutyl) indenyl)(pentamethylcyclopentadienyl)hafnium dichloride,
(1-(1-propyl-1-si lacyclobutyl) indenyl)(pentamethylcyclopentadienyl)hafnium dichloride,
(1-(1-butyl-1-silacyclobutyl)indenyl)(pentamethylcyclopentadienyl)hafnium dichloride,
(1-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)hafnium dichloride,
(1-(1-ethyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)hafnium dichloride,
(1-(1-propyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)hafnium dichloride,
(1-(1-butyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)hafnium dichloride,
(1-methyl-3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)hafnium dichloride,
(1-(1-ethyl-1-silacyclobutyl)-3-methyl-cyclopentadienyl)(cyclopentadienyl)hafnium dichloride,
(1-(1-propyl-1-silacyclobutyl)-3-methyl-cyclopentadienyl)(cyclopentadienyl)hafnium dichloride,
(1-(1-butyl-1-silacyclobutyl)-3-methyl-cyclopentadienyl)(cyclopentadienyl)hafnium dichloride,
((1-methyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclopentadienyl)hafnium dichloride,
((1-ethyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclopentadienyl)hafnium dichloride,
((1-propyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclopentadienyl)hafnium dichloride,
((1-butyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclopentadienyl)hafnium dichloride,
(1-methyl-3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclopentadienyl)hafnium dichloride,
(1-(1-ethyl-1-silacyclobutyl)-3-methyl-cyclopentadienyl)(pentamethylcyclopentadienyl)hafnium dichloride,
(1-methyl-3-(1-propyl-1-silacyclobutyl)cyclopentadienyl)(pentamethylcyclopentadienyl)hafnium dichloride,
(1-(1-butyl-1-silacyclobutyl)-3-methyl-cyclopentadienyl)(pentamethylcyclopentadienyl)hafnium dichloride,
bis(9-(1-methyl-1-silacyclobutyl)-fluorenyl)hafnium dichloride,
bis(9-(1-ethyl-1-silacyclobutyl)-fluorenyl)hafnium dichloride,
bis(9-(1-propyl-1-silacyclobutyl)-fluorenyl)hafnium dichloride,
bis(9-(1-butyl-1-silacyclobutyl)-fluorenyl)hafnium dichloride,
(9-(1-methyl-1-silacyclobutyl)-fluorenyl)(cyclopentadienyl)hafnium dichloride,
(9-(1-ethyl-1-silacyclobutyl)-fluorenyl)(cyclopentadienyl)hafnium dichloride,
(9-(1-propyl-1-silacyclobutyl)fluorenyl)(cyclopentadienyl)hafnium dichloride,
(9-(1-butyl-1-silacyclobutyl)-fluorenyl)(cyclopentadienyl)hafnium dichloride,
(9-(1-methyl-1-silacyclobutyl)-fluorenyl)(pentamethylcyclopentadienyl)hafnium dichloride,
(9-(1-ethyl-1-silacyclobutyl)-fluorenyl)(pentamethylcyclopentadienyl)hafnium dichloride,
(9-(1-propyl-1-silacyclobutyl)-fluorenyl)(pentamethylcyc lopentadienyl)hafnium dichloride,
(9-(1-butyl-1-silacyclobutyl)-fluorenyl)(pentamethylcyclopentadienyl)hafnium dichloride,
dimethylsily(-1-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(tert-butylamido)hafnium dichloride,
dimethylsilyl(1-(1-methyl-1-silacyclobutyl)cyclopentadienyl) (sec-butylamido)hafnium dichloride,
ethylene-bis(1-(1-methyl-1-silacyclobutyl)indenyl)hafnium dichloride,
ethylene-bis(1-(1-ethyl-1-silacyclobutyl) indenyl)hafnium dichloride,
ethylene-bis(1-(1-propyl-1-silacyclobutyl)indenyl)hafnium dichloride,
ethylene-bis(1-(1-butyl-1-silacyclobutyl)indenyl)hafnium dichloride,
ethylene-bis(1-(1-methyl-1-silacyclobutyl)tetrahydroindenyl)hafnium dichloride,
ethylene-bis(1-(1-ethyl-1-silacyclobutyl)tetrahydroindenyl)hafnium dichloride,
ethylene-bis(1-(1-propyl-1-silacyclobutyl)tetrahydroindenyl)hafnium dichloride,
ethylene-bis(1-(1-butyl-1-silacyclobutyl)tetrahydroindenyl)hafnium dichloride,
2,2-propyl-bis(3-(1-methyl-1-silacyclobutyl)-1-indenyl)hafnium dichloride,
2,2-propyl-bis(3-(1-ethyl-1-silacyclobutyl)-1-indenyl)hafnium dichioride,
2,2-propyl-bis(3-(1-butyl-1-silacyclobutyl)-1-indenyl)hafnium dichloride,
2,2-propyl-bis(3-(1-methyl-1-silacyclobutyl)-1-tetrahydroindenyl)hafnium dichloride,
2,2-propyl-bis(3-(1-ethyl-1-silacyclobutyl)-1-tetrahydroindenyl)hafnium dichloride,
2,2-propyl-bis(3-(1-butyl-1-silacyclobutyl)-1-tetrahydroindenyl)hafnium dichioride,
ethylene-bis(3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)hafnium dichloride,
2,2-propyl-bis(3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)hafnium dichioride,
2,2-propyl-(3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(cyclopentadienyl)hafnium dichloride,
2,2-propyl-(3-(1-methyl-1-silacyclobutyl)cyclopentadienyl)(pentamethyl cyclopentadienyl)hafnium dichloride.
The metallocene compounds can be used as catalysts for polymerizing olefin monomers in combination with an activator such as methylaluminoxane (MAO), modified methylaluminoxane (MMAO), aromatic boron compounds substituted with fluoride [for example, tri(butyl)ammonium tetra(pentafluorophenyl)boron, N,N-dimethylanilinium tetra(pentafluorophenyl) boron], or modified clays [for example, N,N-dimethylanilinium montmorillonite, N,N-dimethylanilinium hectorite]. If necessary, the metallocene compounds and activators can be affixed to a solid carrier to form a carrier-supported catalyst.
In the present invention, any aluminoxane and modified aluminoxane available from conventional commercial manufacturer can be used as the activator. The aluminoxane can be prepared by conventional methods such as method of adding appropriate amount of water to trialkylaluminum, method of reacting hydrated hydrocarbon compound or inorganic hydrated salt with trialkylaluminum, and the like. Generally, mixture of linear and ring type aluminoxanes is obtained by the methods. In this invention, linear or ring type oligomer of hydrocarbyl aluminoxane can be used alone or in combination. The representative example of the linear and ring type aluminoxanes are shown in the following formula 4 and 5, respectively. 
In the formula 4 and 5, Rxe2x80x2 is hydrocarbyl radical, preferably, linear or branched alkyl radical having 1 to 10 carbon atoms, more preferably, most of Rxe2x80x2 is methyl, x is an integer of 1 to 50, preferably, 10 to 40, and y is an integer of 3 to 50, preferably, 10 to 40. The aluminoxane is commercially available in the form of hydrocarbon solution. In the present invention, the preferable form of the aluminoxane is an aromatic hydrocarbon solution of the aluminoxane, and the more preferable form is a toluene solution of the aluminoxane.
In combination with the activator, the metallocene compounds of the present invention can be used as catalysts for polymerizing xcex1-olefin having 2 to 12 carbon atoms. In polymerization reaction, the metallocene compound of the present invention can be used in the homogeneous state, in which the metallocene compound and activator are uniformly dissolved in a reactor, and in the carrier supported state, in which the metallocene compound and/or the activator are supported by an inorganic oxide carrier(e.g., silica, alumina, or silica-alumina mixture) as well as in an insoluble particle form. Therefore, the catalyst including the metallocene compound of the present invention and the activator can be applied to various polymerization methods including liquid phase, slurry phase and gas phase olefin polymerization. The polymerization catalysts may include two or more different metallocene compounds of the formula 1 or 2, and can polymerize ethylene, if necessary, in the presence of desired amounts of other kinds of olefins. Other olefins is preferably xcex1-olefin having 3 to 10 carbon atoms, and the more preferable xcex1-olefin include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, 3,4-dimethyl-1-hexene, and their derivatives and mixture.
The conditions of the olefin polymerization can be broadly varied according to the kinds of the olefin and metallocene compound, type of the catalyst being used in the polymerization (homogeneous form or carrier supported form), polymerization method (liquid phase, slurry phase or gas phase polymerization), degree of polymerization, and the like. Usually, the polymerization temperature is in the range of about 20 to about 200xc2x0 C., and the polymerization pressure is in the range of 10 to 7000 psig. The molecular weight of polymer can be controlled by changing the polymerization temperature or injecting hydrogen into the reactor.
The amounts of the catalyst components can be also broadly varied, and the preferable mole ratio of aluminum in the aluminoxane to transition metal in the metallocene compound ([aluminum]: [transition metal]) is in the range of 1:1 to 100,000:1, more preferably, 5:1 to 15,000:1. The olefin polymerization is generally performed in the presence of liquid or gas phase diluent. The diluent should be a non-reactive material to the catalyst system for preventing adverse effect, and substances which deteriorates the catalytic activity of the metallocene compound should be removed from the diluent before the diluent is used in the olefin polymerization. Preferable diluent includes propane, butane, isobutane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, toluene, xylene, their derivatives and their mixture.
Preferred and non-limiting examples will be provided below in order to more fully illustrate the present invention. In the following examples, the metallocene compounds were prepared by the Schlenk method to block air and moisture, and purified and dried nitrogen was used as inert gas. The dichloromethane solvent was dehydrated with calcium hydride, and the other solvents were dehydrated with sodium under inert nitrogen atmosphere before use. Deuterated solvent for Nuclear Magnetic Resonance (NMR) Spectrometry was kept with molecular sieve and used at need.